CN108675632B - Optical glass and optical element - Google Patents
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Abstract
The invention provides an optical glass with a refractive index of 1.65-1.70 and an Abbe number of 48-53. The optical glass comprises the following components in percentage by weight: SiO 22 20‑36％、B2O3 10‑20％、La2O3 10‑22％、ZnO 9‑28％、Nb2O5 0.5‑6％、ZrO2 2‑8％、CaO 7‑16％、Li2O1.5-7%. The Tg temperature of the optical glass is 505-570 ℃, and the expansion coefficient is less than 80 multiplied by 10 when the average value of 20-120 ℃ is taken‑7K; the density is less than 3.55g/cm3Powder method Water stabilityWLeaching percentage less than 0.025, stability against acid action by powder method DAThe leaching percentage is less than 0.50.
Description
The present application is a divisional application of an invention patent application having an application number of 201410292866.4, and an application date of 26/6/2014, and entitled "optical glass and optical element".
Technical Field
The invention relates to optical glass, in particular to optical glass with a refractive index of 1.65-1.70 and an Abbe number of 48-53.
Background
In recent years, optical imaging apparatuses, especially small optical imaging apparatuses such as card cameras, single-cell cameras, camera phones, surveillance cameras, automobile data recorders, etc., have been widely used, and these optical imaging apparatuses mainly have two development trends in the future: firstly, the volume of the camera equipment is smaller and smaller, and the camera equipment can be conveniently coupled with other equipment; and secondly, the imaging quality is higher and higher, and the application requirement of high-definition videos can be met.
From the design of an optical system, the aspheric lens has great advantages compared with a spherical lens, the aspheric surface can improve the relative aperture ratio of the optical system and enlarge the field angle, the used lens number is less than that of the spherical lens while the beam quality is improved, the shape of the lens can be small, and the weight of the system can be reduced; from the aspect of imaging quality, the optical system designed by adopting the aspheric surface technology can eliminate spherical aberration, coma aberration, astigmatism and field curvature and reduce optical energy loss, thereby obtaining high-quality image effect and high-quality optical characteristics.
In the past, the aspheric lens can only be obtained through the traditional grinding and polishing processes, is low in efficiency and high in cost, and can only be applied to high-end optical imaging equipment. In recent years, aspheric surface precision profiling technology has been developed rapidly, and unlike conventional aspheric surface processing technology, the aspheric surface precision profiling technology adopts a method of softening optical glass in a common mold, pressing the optical glass into a preform, and then placing the preform into a mold having a high-precision surface to heat again and press the preform into an aspheric lens. Because the surface precision of the aspheric surface mould is very high, the surface quality of the pressed finished product is very good, and the pressed finished product can be directly installed for use. The manufacturing method has the advantages that the subsequent working procedures such as processing, grinding and the like are reduced, a large amount of cost can be saved, and the emission of harmful substances such as grinding fluid, grinding powder, adhesive and the like used in the subsequent working procedures can be reduced.
The precision mold used in the aspheric surface profiling is generally made of hard and brittle materials, and must be machined by an ultra-precision computer numerical control lathe with the resolution of 0.01 μm, ground into the desired shape precision by a diamond grinding wheel, and polished into an optical mirror surface. Therefore, the precision mold used for the aspherical surface molding is expensive.
If the aspheric surface precision mold works at a higher temperature (more than or equal to 600 ℃), the precision mold is easy to oxidize at a high temperature and cannot be used continuously. Therefore, the primary requirement for optical glass suitable for aspheric precision press molding is that the Tg temperature is lower than 600 ℃, and the lower the Tg temperature, the longer the precision mold life and the lower the production cost of aspheric lenses. Therefore, in recent years, low Tg optical glass has been greatly developed to meet the demand for aspherical precision press molding.
In addition, the mold used in the aspherical surface profiling technology generally has an expansion coefficient of 40 to 50 × 10-7and/K, if the expansion coefficient of the optical glass for profiling is too different from that of the mold, the shrinkage degree of the aspheric lens and the mold is inconsistent in the cooling process, and the defects such as cracks and the like are easily caused.
In the past patent literature, most of these glasses have been based on borate glass systemsAnd adding a certain amount of rare earth oxide, alkaline earth metal oxide and alkali metal oxide. When such a glass system B2O3At a larger content, the chemical stability may be deteriorated. In recent years, after optical elements are finished (i.e., after polishing), it is necessary to clean optical parts before plating. At present, the mainstream cleaning method is ultrasonic cleaning, and water on the surface of a part is evaporated in a drying dish after the cleaning is finished. During this process, the surface of the part is exposed to water for a certain period of time. In addition, CO in the air2The gas and water on the surface of the glass form weakly acidic carbonic acid. Therefore, if the water resistance and acid resistance of the glass are poor, the polished layer of the glass is damaged, which causes difficulty in the subsequent coating process. Therefore, the optical glass itself needs to have better chemical stability, so as to improve the yield in the later processing and coating processes.
For low Tg glass, in order to lower the glass Tg, it is necessary to introduce large amounts of alkali metals into the glass system to disrupt the glass network, resulting in a lowering of the glass Tg. However, the chemical stability of the glass is drastically reduced while the glass network is broken. Therefore, ensuring the chemical stability of the glass while achieving a lower Tg temperature is a challenge for developing low Tg optical glasses.
Chinese patent 200780006104.1 describes an optical glass with refractive index of 1.65-1.72 and Abbe number of 47-57, which contains 30-40% of B2O3And 15-25% Gd2O3，SiO2Is an optional added component. B of the glass2O3Higher levels result in less chemical stability of the glass, especially less stability against water. In addition, Gd2O3Is a noble oxide, and the addition of a large amount of the noble oxide causes the cost of the glass to rise.
Chinese patent 200810236827.7 describes an optical glass with refractive index of 1.69-1.74 and Abbe number of 41-47, and SiO2/B2O3Is less than 4, which indicates that B2O3Is a main network formerThe stability of the study is greatly affected.
Chinese patent 98108717.5 describes an optical glass with a refractive index of 1.67-1.75 and an Abbe number of 42-50, which contains 1-7% TiO2This causes a decrease in the ultraviolet transmittance of the glass. In addition, the glass also contains 26-38% of BaO, and the addition of a large amount of BaO is disadvantageous for reducing the density of the glass.
Disclosure of Invention
The invention aims to solve the technical problem of providing optical glass with the refractive index of 1.65-1.70 and the Abbe number of 48-53.
The technical scheme adopted by the invention for solving the technical problem is as follows: the optical glass comprises the following components in percentage by weight: SiO 22 20-36％、B2O3 10-20％、La2O3 10-22％、ZnO 9-28％、Nb2O5 0.5-6％、 ZrO2 2-8％、CaO 7-16％、Li2O 1.5-7％。
Further, the SiO2In an amount greater than B2O3The content of (a).
Further contains 0-6% of SrO, 0-6% of MgO and Na2O 0-3％、K2O 0-3％、Sb2O3 0-0.2％。
Further, the weight percentage composition is as follows: SiO 22 20-36％、B2O3 10-20％、La2O3 10-22％、ZnO 9-28％、Nb2O5 0.5-6％、ZrO2 2-8％、CaO 7-16％、Li2O 1.5-7％、 SrO 0-6％、MgO 0-6％、Na2O 0-3％、K2O 0-3％、Sb2O3 0-0.2％。
Further, wherein SiO222-34%, and/or B2O311-18%, and/or La2O311-20%, and/or ZnO 10-26%, and/or Nb2O51-5%, and/or ZrO23-7%, and/or CaO 8-15%, and/or Li2O 2-6％。
Further, SrO is 0-4%, and/or MgO is 0-4%.
Further, wherein BaO and/or Na are not contained2O, and/or K2O, and/or Sb2O3。
Further, the glass transition temperature is 505-570 ℃.
Furthermore, the expansion coefficient of the glass is less than 80 multiplied by 10 when the average value of 20-120 ℃ is taken-7/K。
Furthermore, the glass has a refractive index of 1.65-1.70 and an Abbe number of 48-53.
Further, the density of the glass is less than 3.55g/cm3。
Further, the powder method water-resistant action stability D of the glassWThe leaching percentage is less than 0.025; stability to acid action by powder method DAThe leaching percentage is less than 0.50.
The prefabricated member made of the optical glass is adopted.
An optical element made of the above optical glass.
The invention has the beneficial effects that: the Tg temperature of the optical glass is 505-570 ℃, and the expansion coefficient is less than 80 multiplied by 10 when the average value of 20-120 ℃ is taken-7K; the density is less than 3.55g/cm3Powder method Water stabilityWLeaching percentage less than 0.025, stability against acid action by powder method DAThe leaching percentage is less than 0.50.
Detailed Description
The reason for the selection of the various oxides and the addition ranges in the present invention is described below, and the contents of the respective components are expressed in weight% unless otherwise specified.
SiO2In the present invention, the main network former of the glass is limited to 20 to 36%, preferably 22 to 34%. When the content thereof is less than 20%, the glass is easily devitrified and the chemical stability is remarkably decreased; when the content exceeds 36%, the melting is difficult, and the melting is difficult to perform with La2O3In the coexistence, glass is easily devitrified.
B2O3Also in the present invention is a network former of glass, which is effectively reduced when added to glassLow melting temperature. The pure borate system glass has poor chemical stability, small high-temperature viscosity and easy devitrification. This is because if there is no SiO in the glass2Or SiO2In the case of a smaller content, B2O3Boron-oxygen trigones, which are poor in stability, are mainly present in the glass. When SiO is present2When the content of (2) is gradually increased, the boron-oxygen triangle is gradually changed into the boron-oxygen tetrahedron, and the broken net of the glass network is reduced, so that the chemical stability of the glass is improved, and the devitrification resistance of the glass can be improved.
However, SiO2The more the amount of the compound (A) is, the better the SiO content is2When the amount of (A) exceeds a certain amount, not only does the glass melting temperature rise, but the continued increase in siloxatetrahedra leads to the occurrence of silicon-rich crystalline phases, which in turn lead to devitrification of the glass. Therefore, the present inventors have made extensive studies to find that when SiO is used2When the limit is 20-36%, B2O3Is limited to a range of 10 to 20% and satisfies SiO2The content is more than B2O3The content of the glass can ensure that the glass obtains better chemical stability, devitrification resistance and smaller expansion coefficient. B is2O3The content of (B) is preferably 11 to 18%.
La2O3The oxide is a high-refraction low-dispersion oxide, and the refractive index of the glass can be obviously improved when the oxide is added into the glass. In the present invention, La2O3If the content of (b) is less than 10%, the glass cannot reach the designed optical constant; if the content is more than 22%, phase separation tends to occur to cause devitrification. Therefore, the content thereof is limited to 10 to 22%, preferably 11 to 20%.
The addition of ZnO to the glass can adjust the refractive index and dispersion of the glass. Of particular importance is the addition of ZnO to such glass systems to enhance the glass forming ability of the glass system. In addition, the addition of ZnO lowers the Tg of the glass. If the ZnO content is less than 9 percent, on one hand, the glass forming capability is reduced, and on the other hand, the dispersion of the glass can not meet the design requirement; if the ZnO content is more than 28%, the devitrification resistance of the glass is lowered, and the glass has a low viscosity at a forming temperature and is liable to generate striae. Accordingly, the content of ZnO is 9 to 28%, preferably 10 to 26%.
Nb2O5Is a high-refraction high-dispersion oxide, and plays a role in adjusting optical constants in the invention. If the content is less than 0.5% or more than 6%, the Abbe number of the glass does not satisfy the design requirement, and therefore, the content is limited to 0.5 to 6%, preferably 1 to 5%.
ZrO2The glass is added to improve the refractive index and dispersion of the glass, and can obviously improve the chemical stability of the glass. In the glass component of the invention, if the content is less than 2%, the chemical stability improvement effect is not obvious; however, if the content is more than 8%, the melting of the molten glass becomes difficult and the glass is easily devitrified. Therefore, the content thereof is limited to 2 to 8%, preferably 3 to 7%.
The alkaline earth metal compounds CaO, MgO, SrO and BaO are added into the glass, so that the optical constants of the glass can be adjusted, and the melting assisting effect can be achieved. In addition, the addition of an appropriate amount can adjust the expansion coefficient, chemical stability, and the like of the glass. Although the density of BaO is significantly higher than the other three species for the congeneric alkaline earth metal oxides, if BaO is added to the glass of the present invention, the density of the glass increases significantly. Meanwhile, BaO-containing glasses are more susceptible to attack in the presence of acidic conditions (e.g., wet weather) than other alkaline earth oxides. Therefore, BaO is not added in the present invention.
In order to obtain glass with low density and adjust the expansion coefficient, chemical stability and the like of the glass, CaO with the content of 7-16% is added, and the preferable content is 8-15%; the content of SrO is 0-6%, and the preferable content is 0-4%; the MgO content is 0-6%, preferably 0-4%.
Li2O、Na2O、K2O is also an alkali metal oxide. The alkali metal oxide added into the glass can play a role in melting, and the melting temperature of the glass is reduced, so that the glass is easy to melt. From the aspect of glass structure, alkali metal ions enter the glass and can break the glass network. The proper breaking of the glass network can reduce the high temperature viscosity of the glass and lower the Tg temperature of the glass. However, ifExcessive alkali metal oxide enters the glass, the glass network is seriously damaged, and the chemical stability, the anti-crystallization performance and the like of the glass are greatly reduced. Therefore, the selection of proper types and contents of alkali metal oxides plays a very important role in realizing the balance of six aspects of smelting process, glass viscosity, chemical stability, anti-devitrification performance, glass Tg temperature, glass expansion coefficient and the like.
In the glass system described in the invention, repeated tests by the inventor show that under the same percentage content of Li2The strongest ability of O to break the glass network, with Na2O and K2The ability to lower the glass Tg is strongest compared to O. Of particular importance are those with Na+1And K+1Ion phase ratio, Li+1The field intensity is larger, the gathering ability to the surrounding ions is stronger than that of other two alkali metal ions, and the glass expansion coefficient can be reduced under the condition of the same content. Thus, in the glass system described in the present invention, Li2If the content of O is less than 1.5%, the effect of lowering the Tg of the glass is not significant; if the content is more than 7%, the glass network is seriously damaged, and devitrification and chemical stability of the glass are easily reduced. Therefore, the content thereof is limited to 1.5 to 7%, preferably 2 to 6%.
After addition of Li2Optionally adding small amount of Na while adding O2O and K2O, which serves to balance the glass components. Thus, Na2The content of O is limited to 0-3%, preferably no addition; k2The O content is limited to 0 to 3%, and preferably no addition is made.
In order to improve the bubble removal capability of the glass in the smelting process, 0-0.2% of Sb can be added2O3The use of a clarifying agent is preferably not added.
The properties of the glasses described in the present invention were measured using the following test methods.
The refractive index and Abbe number of the glass are measured by GB/T7962.11-2010 test standard.
The glass Tg temperature was measured using the GB/T7962.16-2010 test standard.
The coefficient of thermal expansion of the glass is measured using the GB/T7962.11-2010 test standard, and the values given herein represent the average coefficient of thermal expansion over a temperature range of 20-120 ℃.
The glass density was measured using the GB/T7962.20-2010 test standard.
The stability of the water-resistant effect of the glass DW is measured by using the GB/T17129 test standard.
The acid resistance stability DA of the glass is measured by using GB/T17129 test standard.
Through tests, the optical glass of the invention has the following properties: a refractive index (nd) of 1.65 to 1.70, an Abbe number (vd) of 48 to 53, and a density (. rho.) of 3.55g/cm3The Tg temperature is 505-570 ℃, and the expansion coefficient (average value at 20-120 ℃) is less than 80 multiplied by 10-7K, stability to water action by powder method DWThe leaching percentage is less than 0.025; stability to acid action by powder method DAThe leaching percentage is less than 0.50.
The present invention also provides an optical preform and an optical element formed from the above optical glass according to methods well known to those skilled in the art. Since the optical glass has a high refractive index and high dispersion, the optical element also has a high refractive index and high dispersion, and can be applied to digital cameras, digital video cameras, camera phones, vehicle-mounted image pickup devices, monitoring devices, and the like.
Examples
In order to further understand the technical solution of the present invention, examples of the optical glass of the present invention will now be described. It should be noted that these examples do not limit the scope of the present invention.
The optical glasses (examples 1 to 20) shown in tables 1 to 2 were obtained by weighing and mixing general raw materials (such as oxides, hydroxides, carbonates, nitrates, etc.) for optical glasses in the ratios of the respective examples shown in tables 1 to 2, placing the mixed raw materials in a platinum crucible, melting at 1260 ℃ to 1300 ℃ for 2.5 to 4 hours, and after clarification, stirring and homogenization, obtaining a homogeneous molten glass free from bubbles and undissolved substances, casting the molten glass in a mold and annealing.
The compositions of examples 1 to 20 are shown in tables 1 to 2 together with the results of refractive index (nd), Abbe number (vd), density (. rho.), Tg temperature, expansion coefficient, percent leaching against water action, percent leaching against acid action, and the like. In these tables, the compositions of the respective components are expressed in% by weight.
TABLE 1
TABLE 2
Claims (10)
1. The optical glass is characterized by comprising the following components in percentage by weight: SiO 22：20-36％、B2O3：10-20％、La2O3：10-22％、ZnO：9-28％、Nb2O5：0.5-6％、ZrO2：2-8％、CaO：7.2-13.7％、Li2O：1.5-7％、SrO：0-6％、MgO：0-6％、Na2O：0-3％、K2O：0-3％、Sb2O3：0-0.2％。
2. The optical glass of claim 1, wherein the SiO is2In an amount greater than B2O3The content of (a).
3. The optical glass of claim 1, wherein: SiO 22: 22-34%, and/or B2O3: 11-18%, and/or La2O3: 11-20%, and/or ZnO: 10-26%, and/or Nb2O5: 1-5%, and/or ZrO2: 3-7%, and/or CaO: 8-13.7%, and/or Li2O: 2-6%, and/or SrO 0-4%, and/or MgO 0-4%.
4. The optical glass according to claim 1, wherein BaO is not containedAnd/or Na2O, and/or K2O, and/or Sb2O3。
5. An optical glass according to claim 1, wherein the glass has a refractive index of 1.65 to 1.70 and an Abbe number of 48 to 53.
6. The optical glass according to claim 1, wherein the glass transition temperature is from 505 ℃ to 570 ℃.
7. An optical glass according to claim 1, characterised in that the glass has a coefficient of expansion, on average at 20-120 ℃, of less than 80 x 10-7K; the density of the glass is less than 3.55g/cm3。
8. The optical glass according to claim 1, wherein the glass has a powder-process water-resistance stability DWThe leaching percentage is less than 0.025; stability to acid action by powder method DAThe leaching percentage is less than 0.50.
9. A preform made of the optical glass according to any one of claims 1 to 8.
10. An optical element produced by using the optical glass according to any one of claims 1 to 8.
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| CN201410292866.4A CN105271714A (en) | 2014-06-26 | 2014-06-26 | Optical glass and optical element |
| CN201810620443.9A CN108675632B (en) | 2014-06-26 | 2014-06-26 | Optical glass and optical element |
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| US4481299A (en) * | 1981-10-01 | 1984-11-06 | Hoya Corporation | Optical glass |
| JPH0492834A (en) * | 1990-08-02 | 1992-03-25 | Sumita Kogaku Glass:Kk | Optical glass for precise press |
| JP2002029773A (en) * | 2000-07-06 | 2002-01-29 | Senyo Glass Kogyo Kk | Glass composition |
| CN101012102A (en) * | 2006-02-02 | 2007-08-08 | 株式会社小原 | Optical glass |
| CN102167508A (en) * | 2010-12-17 | 2011-08-31 | 成都赛林斯科技实业有限公司 | Optical glass with high refraction index and manufacturing method thereof |
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| FR2590888A1 (en) * | 1985-11-29 | 1987-06-05 | Corning Glass Works | LOW-DENSITY, HIGH-REFRACTIVE LOW-DISPERSION OPHTHALMIC LENSES |
| JP2008179500A (en) * | 2007-01-24 | 2008-08-07 | Konica Minolta Opto Inc | Optical glass and optical device |
| JP2009173520A (en) * | 2007-10-30 | 2009-08-06 | Nippon Electric Glass Co Ltd | Optical glass for mold press forming |
| CN101445322A (en) * | 2008-12-30 | 2009-06-03 | 成都光明光电股份有限公司 | Dense crown optical glass |
| CN101508522A (en) * | 2009-03-27 | 2009-08-19 | 成都光明光电股份有限公司 | Accurate die pressing optical glass |
| CN101941795A (en) * | 2009-07-10 | 2011-01-12 | 湖北新华光信息材料股份有限公司 | High-refractive-index optical glass |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4481299A (en) * | 1981-10-01 | 1984-11-06 | Hoya Corporation | Optical glass |
| JPH0492834A (en) * | 1990-08-02 | 1992-03-25 | Sumita Kogaku Glass:Kk | Optical glass for precise press |
| JP2002029773A (en) * | 2000-07-06 | 2002-01-29 | Senyo Glass Kogyo Kk | Glass composition |
| CN101012102A (en) * | 2006-02-02 | 2007-08-08 | 株式会社小原 | Optical glass |
| CN102167508A (en) * | 2010-12-17 | 2011-08-31 | 成都赛林斯科技实业有限公司 | Optical glass with high refraction index and manufacturing method thereof |
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| CN105271714A (en) | 2016-01-27 |
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